Polyether urethane foam

ABSTRACT

A process for producing high resilience polyether urethane foam using a cyanoalkoxy-alkyl modified siloxane fluid; the foams derived therefrom; a solvent-solution of said siloxane; and cyanoalkoxy-alkyl modified siloxane fluids per se.

This application is a continuation-in-part of application Ser. No.334,767, filed Feb. 22, 1973, now abandoned.

BACKGROUND OF THE INVENTION

This invention relates to high resilience polyurethane foams and moreparticularly to the use of certain organosilicon polymers in theproduction of such foams.

Basically such high resilience foams are produced by the reaction ofhighly primary hydroxyl-capped, high molecular weight polyols withorganic isocyanates and water. High resilience polyurethane foams aredistinguishable in part from conventional hot cure polyurethane foams bythe use of such polyols and the fact that high resilience polyurethanefoams require little or no oven curing and thus are often referred to ascold cure foams. Such foams are extremely desirable for cushioningapplications because of their excellent physical properties, e.g. veryhigh foam resiliency, low flammability, opencelled structure, low flexfatigue (long life) and high SAC factors (load bearing properties).

Because of the high reactivity of high resilience foam ingredients andtheir rapid buildup of gel strength, sometimes the foam can be obtainedwithout a cell stabilizer, however such foams typically have veryirregular cell structure as particularly evidenced by surface voids andthe discovery of a proper agent to help control cell structure hasremained a major problem in the art.

Attempts to solve this problem with surfactants generally employed inthe stabilization of hot cure polyurethane foam have not provensatisfactory because such surfactants tend to overstabilize, causingextremely tight, shrinkaging foam. Nor is the problem corrected byreducing the concentrations of such surfactants, since at concentrationsrequired to eliminate shrinkage, the cells are no longer stabilizedsatisfactorily and the foam structure becomes irregular, coarse andcontains surface voids.

The use of low viscosity dimethylsilicone oils alone as stabilizers forhigh resilience foams also has various disadvantages. For example, atlow concentrations they create metering and pumping problems in theprocessing of the foam, while at higher concentrations these oilsadversely affect the physical properties of the foam. Solvents for suchdimethylsiloxane oils that are non-reactive with the foam ingredientse.g. alkanes, hexamethyldisiloxane, and the like, can adversely affectthe foam's physical properties in proportion to their concentration andgenerally create flammability hazards. Furthermore isocyanate reactivediluents, such as polyether triols and the like which do notsignificantly change the foam's properties, inasmuch as they react intothe system and become part of the foam structure, are not satisfactorysolvents for dimethylsilicone oils, since not enough oil can bedissolved to provide foam stabilization at practical solutionconcentrations. High resilience foams are also adversely affected bydimethylsilicones having more than about ten dimethylsiloxy units persiloxane. For example only five or ten weight per cent of such speciesin a dimethyl silicone oil can appreciably degrade the foam's physicalproperties and even cause foam shrinkage.

Moreover, while particularly unique high resilience polyether urethanefoam can be prepared employing certain siloxane-oxyalkylene blockcopolymers as disclosed in U.S. Pat. application Ser. No. 84,181 filedOct. 26, 1970, now U.S. Pat. No. 3,741,917, or certain aralkyl modifiedsiloxane polymers as disclosed in U.S. Pat. application Ser. No. 305,713filed Nov. 13, 1972, now U.S. Pat. No. 3,839,384, or certain cyanoalkylmodified siloxane fluids as disclosed in my copending U.S. applicationSer. No. 325,327 filed Jan. 22, 1973, now abandoned said disclosures donot teach the use of the novel organosilicon polymers employed in thisinvention.

SUMMARY OF THE INVENTION

It has been discovered that flexible high resilience polyether urethanefoam can be prepared according to the instant invention which involvesemploying certain novel siloxane polymer fluids as more fully definedbelow.

The siloxane polymer fluids employed in this invention have been foundto control the cell uniformity of high resilience polyether urethanefoam without obtaining tight foam and without introducing foam shrinkageor causing any severe adverse effects to the foam's physical properties,e.g. the foam's resilience and its resistance towards flammability.Moreover voids in the foam are eliminated or at least greatly reduced bythe instant invention and the cell structure of the foam is also muchmore uniform and finer than where no stabilizing agent is employed. Thisdiscovery is surprising since as outlined above not all surfactants areso suitable for use in the production of high resilience foams. Indeedeven siloxane polymer fluids of the same type employed herein, butoutside the scope of the instant invention, were found to causeshrinkage of the foam.

Therefore it is an object of this invention to provide a process forproducing high resilience polyether urethane foam. It is further anobject of this invention to provide novel organosilicon fluids for usein said process. It is still another object of this invention to providenovel compositions of said fluids for use in said process. It is alsoanother object of this invention to provide high resilience polyetherurethane foams produced by said process. Other objects and advantages ofthis invention will become readily apparent from the followingdescription and appended claims.

More particularly this invention is directed, in part, to a process forpreparing high resilience polyether urethane foam, said processcomprising foaming and reacting a reaction mixture comprising:

I. an organic polyol selected from the group consisting of (A) apolyether triol containing at least 40 mole percent primary hydroxylgroups and having a molecular weight from about 2,000 to about 8,000 and(B) a mixture of said polyether triol and other polyethers having anaverage of at least two hydroxyl groups, said polyether triol of saidmixture amounting to at least 40 weight percent of the total polyolcontent;

II. an organic polyisocyanate, said organic polyol and saidpolyisocyanate being present in the mixture in a major amount and in therelative amount required to produce the urethane;

III. a blowing agent in a minor amount sufficient to foam the reactionmixture;

IV. a catalytic amount of a catalyst for the production of the urethanefrom the organic polyol and polyisocyanate; and

V. a minor amount of a cyanoalkoxy-alkyl modified siloxane fluid havingthe average formula

    (X).sub.z R.sub.3.sub.-z SiO(R.sub.2 SiO).sub.x [(X)(R)SiO].sub.Y SiR.sub.3.sub.-z X.sub.z

wherein x has a value of 2 to 6 inclusive; y has a value of 0 to 6inclusive; z has a value of 0 to 1 inclusive; R is a lower alkyl orphenyl radical; and X is a cyanoalkoxy-alkyl radical of the formula--(O)_(n) R'OR"CN wherein n has a value of 0 or 1, R' is an alkyleneradical having from 3 to 8 carbon atoms and R" is an alkylene radicalhaving from 2 to 4 carbon atoms; said siloxane fluid containing at leastone of said cyanoalkoxy-alkyl radicals and having an average molecularweight in the range of about 400 to 2000.

It is to be understood of course that the above process and the appendedclaims read on employing a single ingredient of the type specified orany of the various combinations of ingredient mixtures possible. Forexample, in addition to employing a single ingredient of the typesspecified, if desired, a mixture of triols, a mixture ofpolyisocyanates, a mixture of blowing agents, a mixture of catalystsand/or a mixture of siloxane fluids can be employed. Likewise thetriol-polyether starting mixture could consist of a single triol and amixture of polyethers, a mixture of triols and a single polyether or amixture of two or more triols and two or more polyethers.

DESCRIPTION OF THE PREFERRED EMBODIMENTS

As indicated above the cyanoalkoxy-alkyl modified siloxane fluidcompounds employed as the siloxane stabilizers for cell control in thisinvention are characterized as having an average molecular weight range,as containing internal dihydrocarbyl siloxy units (R₂ SiO) and havingsiloxy units containing a cyanoalkoxy-alkyl radical[(NCR"OR'(O)_(n))SiO]. It is of course to be understood that theindividual internal siloxy units can be the same or different and can bearranged in any order. Subject to the above qualifications, a moredetailed description of the cyanoalkoxy-alkyl modified siloxane fluidsis presented below.

Accordingly the siloxane surfactants useful in this invention containinternal dihydrocarbyl siloxy units, such as dimethylsiloxy,diethylsiloxy, dipropylsiloxy, methylethylsiloxy, methylphenylsiloxygroups and the like. Examples of internal cyanoalkoxy-alkyl siloxy unitsthat can be present in said siloxanes include, e.g. 3-(2-cyanoethoxy)propylmethylsiloxy, 3-(2-cyanoethoxy) propyloxymethylsiloxy,3-(2-cyanoethoxy)propylethylsiloxy,3-(2-cyanoethoxy)-2-methylpropylmethyl-siloxy, 8-(2-cyanoethoxy)octylmethylsiloxy, 3-(2-cyano-2-methylethoxy) propylmethylsiloxy,3-(2-cyano-2-ethylethoxy) propylmethylsiloxy, and the like. Illustrativeend-blocking or chain terminating siloxy units of said siloxanes aresuch terminal groups as trimethylsiloxy, triethylsiloxy,(3-(2-cyanoethoxy) propyl) dimethylsiloxy, (3-(2-cyanoethoxy) propyloxy)dimethylsiloxy, (3-(2-cyanoethoxy)-2-methylpropyl) dimethylsiloxy,(3-(2-cyano-2 -methylethoxy) propyl) dimethylsiloxy groups, and thelike. Preferably R is a methyl radical. Thus illustrative of the morepreferred polymeric siloxane fluids employed in the instant inventionare trimethyl end-blocked 3-(2-cyanoethoxy)propylmethylsiloxy-dimethylsiloxanes, trimethyl end-blocked3-(2-cyanoethoxy) propyloxymethylsiloxy-dimethylsiloxanes, trimethylend-blocked3-(2-cyanoethoxy)-2-methylpropylmethylsiloxy-dimethylsiloxanes,trimethyl end-blocked 3-(2-cyano-2-methylethoxy) propylmethylsiloxydimethylsiloxanes, trimethyl end-blocked 8-(2-cyanoethoxy)octylmethylsiloxy dimethylsiloxanes, (3-(2-cyanoethoxy) propyl) dimethylend-blocked dimethylsiloxanes, (3-(2-cyanoethoxy) propyloxy) dimethylend-blocked dimethylsiloxanes, trimethyl end-blocked (3-(2-cyanoethoxy)propylmethylsiloxy)(3-(2-cyanoethoxy)-2-methylpropylmethylsiloxy)-dimethylsiloxanes,(3-(2-cyanoethoxy) propyl) dimethyl end-blocked (3-(2-cyanoethoxy)propylmethylsiloxy) dimethylsiloxanes, (3-(2-cyanoethoxy) propyloxy)dimethyl end-blocked (3-(2-cyanoethoxy) propyloxymethylsiloxy)dimethylsiloxanes, and the like. Most preferably the cyanoalkoxy-alkylradical is bonded directly to the silicon atom through one of its carbonatoms, i.e. Si-C and not through an oxygen atom, i.e. Si-O-C.

Furthermore it is considered that the above cyanoalkoxy-alkyl modifiedsiloxane fluids having an average molecular weight in the range of about400 to about 2000 employed as the cell stabilizers in this invention arenovel compounds per se. The preferred siloxane fluids are those havingan average molecular weight range of about 500 to about 1000, especiallythe trimethyl end-blocked(3-(2-cyanoethoxy)propylmethylsiloxydimethylsiloxanes.

The siloxane fluids of this invention can be produced by any number ofconventional methods well known in the art, as shown e.g. by U.S. Pat.No. 2,872,435 and U.S. application Ser. No. 279,883 filed Aug. 11, 1972,now U.S. Pat. No. 3,846,462. Preferably the siloxane fluids containingnon-hydrolyzable cyanoalkoxy-alkyl radicals (Si-R'OR"CN) are prepared bythe platinum catalyzed addition of an olefinic cyano-substituted ether,e.g. allyl-beta-cyanoethylether, to the corresponding hydrosiloxane attemperatures of generally about 80°C. to 90°C. Such platinum catalystsand platinum derivatives are well known in the art, chloroplatinic acidis particularly effective. The platinum catalyst is convenientlyemployed as a solution for example in tetrahydrofuran, ethanol, butanolor mixed solvents such as ethanol-ethylene glycol dimethyl ether. Thegeneral preferred concentration of platinum in the catalyst based on thetotal weights of siloxane and olefinic derivatives is about 5 to 100parts per million, although higher and lower concentrations may be used.Generally in carrying out the process it is preferred to mix all theingredients, except the platinum catalyst, at about 25°C. and allow themixture to warm up to about 80°C. with external heating and at thistemperature add the platinum catalyst. An exothermic reaction is usuallyobserved. The preferred temperature range for the platinum catalyzedaddition process is generally from about 60°C. to 140°C. Lowertemperatures may be used but the reaction times are slower. Highertemperatures may also be used, e.g. up to 200°C. but offer no apparentadvantage. The choice of solvent if used should of course be adapted tothe preferred temperature range. The removal or neutralization of theplatinum (e.g. chloroplatinic acid) catalyst is desirable for long rangeproduct stability. Usually sodium bicarbonate is added to the reactionmixture to effect neutralization and the resultant slurry filtered. Ofcourse it is preferred to use a stoichiometric excess of the olefiniccyano-substituted ether to insure complete reaction of all of thesilicon-hydrogen bonds. Alternatively the siloxane fluids containingsuch non-hydrolyzable cyanoalkoxy-alkyl radicals may also be prepared bythe equilibration of corresponding siloxanes, e.g. hexamethyldisiloxane,cyclic dimethylsiloxanes and tetracyclic 3-(2-cyanoethoxypropylmethylsiloxane, using an acid or base catalyst. For instance theycan be prepared by equilibration using acid catalysts such as anhydroustrifluoromethyl sulfonic acid, sulfuric acid and the like inconcentrations of about 0.1 to 2.0 weight per cent. The equilibration isgenerally run at temperatures of about 25°C. to 50°C. with vigorousstirring at least until the mixture has become homogeneous. Saidsiloxane fluids can also be prepared by equilibration using a basecatalyst, e.g. potassium silanolate, cesium hydroxide and tetramethylammonium silanolate. Such catalysts are normally employed inconcentrations of 30-200 ppm as potassium equivalent. The equilibrationtemperature depends on the catalyst employed. For instance, withtetramethyl ammonium silanolate a temperature of about 75° C. to 100°C.is sufficient, preferably about 85°C. to 90°C., while the other alkalinecatalysts usually require a temperature of at least about 150°C.Generally the equilibration time is less than 5 hours.

The siloxane fluids containing hydrolyzable cyanoalkoxy-alkyl radicals(SiOR'OR"CN) can be prepared by the catalyzed addition ofcyano-substituted hydroxyl terminated ethers of the formula HOR'OR"CN,e.g. HOC₃ H₆ OC₂ H₄ CN, to the corresponding hydrosiloxanes. Saidaddition type process is conventional and can be promoted by a varietyof catalysts such as organic derivatives of tin, platinum and othertransition metals. Preferred are the organic derivatives of tin such astin carboxylates, e.g. stannous octoate, stannous oleate, stannouslaurate, dibutyl tin dilaurate and the like. The catalysts are generallyused in amounts of about 0.1 to 5, usually no more than about 2, weightper cent, based on the total weight of the reactants. The reactiontemperature generally ranges from about 60°C. to 150°C. (usually 80°C.to 120°C.). Such siloxane fluids may also be prepared, if desired byreacting the cyano-substituted hydroxyl terminated ethers with thecorresponding alkoxysubstituted siloxanes in the presence of a catalystsuch as trifluoroacetic acid and the like. Of course it is preferred touse a stoichiometric excess of cyano-hydroxyl terminated ethers toinsure complete reaction of all of the silicon-hydrogen bonds.

The starting materials for the above processes as well as methods fortheir preparation are of course all well known in the art. It is to beunderstood, of course, that while the siloxane fluids used in thisinvention can be discrete chemical compounds they are usually mixturesof various discrete siloxane species, due at least in part, to the factthat the starting materials used to produce the siloxane fluids arethemselves usually mixtures. Thus, it is to be also understood that theabove average formula representing the siloxane fluids as used hereinincompasses the presence of dihydrocarbon siloxanes as in the case ofunsparged equilibrated products and the possibility of the presence ofsmall amounts of other siloxy units, such as methyl (hydrogen) siloxygroups, in the siloxane polymers due to an incomplete reaction or thenature of the starting materials used to produce the siloxanes. Moreoverthe siloxane fluids employed herein need not be fractionated, as bydistillation but may be sparged (i.e. stripped of lites) or unsparged.

The amount of active cyanoalkoxy-alkyl modified siloxane employed as thefoam stabilizer may fall within the range of about 0.03 to about 2 partsby weight or greater, per hundred parts by weight of the organic polyolstarting material. Preferably the siloxane fluids are employed inamounts ranging from about 0.08 to 0.6 parts by weight per 100 parts byweight of the organic polyol starting materials.

The polyhydroxyl reactants (organic polyols) employed in this inventionas the starting materials to prepare the polyurethane foams can be anypolyether triol containing at least 40 mole percent of primary hydroxylgroups and having a molecular weight from about 2,000 to about 8,000.Conversely said polyether triols can contain no more than 60 mole percent of secondary hydroxyl groups. Preferably said polyether triolscontain about 60 to 90 mole per cent of primary hydroxyl groups and havea molecular weight from about 4,000 to about 7,000.

The preferred polyether triols of this invention are polyalkylencethertriols obtained by the chemical addition of alkylene oxides totrihydroxyl organic containing materials, such as glycerol;1,2,6-hexanetriol; 1,1-trimethylolethane; 1,1,1-trimethylolpropane;3-(2-hydroxyethoxy)-1,2-propanediol;3-(2-hydroxypropoxy)-1,2-propanediol;2,4-dimethyl-2-(2-hydroxyethoxy)methylpentanediol-1,5;1,1,1-tris[(2-hydroxy-ethoxy)methyl] ethane;1,1,1-tris[(2-hydroxypropoxy)methyl]-propane; and the like, as well asmixtures thereof.

Alternatively the organic polyol starting materials of this inventioncan be mixtures consisting essentially of said above defined polyethertriols and other polyether polyols having an average of at least twohydroxyl groups, said above defined polyether triols amounting to atleast 40 preferably at least 50, weight per cent of the total polyolcontent of the mixtures. Illustrative of such other polyethers aretriols outside of the scope defined above, diols, tetraols andpolymer/polyols, and the like, as well as mixtures thereof.

Examples of such polyether polyols that can be mixed with the abovedefined polyether triols include those adducts of alkylene oxide to suchpolyols as diethylene glycol; dipropylene glycol; pentaerythritol;sorbitol; sucrose; lactose; alpha-methylglucoside;alphahydroxylalkylglucoside; novolac resins; water; ethylene glycol;propylene glycol; trimethylene glycol; 1,2-butylene glycol;1,3-butanediol; 1,4-butanediol; 1,5-pentanediol; 1,2-hexane glycol;1,10-decanediol; 1,2-cyclohexanediol; 2-butene-1,4-diol;3-cyclohexene-1,1-dimethanol; 4-methyl-3-cyclohexene-1,1-dimethanol;3-methylene-1,5-pentanediol; (2-hydroxyethoxy)-1-propanol;4-(2-hydroxyethoxy)-1-butanol; 5-(2-hydroxypropoxy)-2-octanol;3-allyloxy-1,5-pentanediol; 2-allyloxymethyl-2-methyl-1,3-propanediol;[4,4-pentyloxymethyl]-1, 3-propane-diol;3-(o-propenyl-phenoxy)1,2-propanediol;2,2-diisopropylidenebis(p-phenyleneoxy)-diethanol; and the like, orphosphoric acid; benzenephosphoric acid; polyphosphoric acids such astripolyphosphoric acid and tetrapolyphosphoric acid; and the like; aswell as mixtures thereof.

Another type of polyether polyol that can be mixed with the abovedefined polyether triols and used as the starting materials of thisinvention are graft polymer/polyether compositions obtained bypolymerizing ethyleneically unsaturated monomers in a polyether asdescribed in British Pat. No. 1,063,222 and U.S. Pat. No. 3,383,351, thedisclosures of which are incorporated herein by reference thereto.Suitable monomers for producing such compositions include, for example,acrylonitrile, vinyl chloride, styrene, butadiene, vinylidine chloride,and the like. Suitable polyethers for producing such compositionsinclude, for example those polyethers hereinabove-described. These graftpolymer/polyether compositions can contain from about 1 to about 70weight per cent, preferably about 5 to about 50 weight per cent and mostpreferably about 10 to about 40 weight per cent of the monomerpolymerized in the polyether. Such compositions are convenientlyprepared by polymerizing the monomers in the selected polyether at atemperature of 40° to 150°C. in the presence of a free radicalpolymerization catalyst, such as peroxides, persulfates, percarbonates,perborates and azo compounds as more fully described by the above patentreferences. The resulting compositions may contain a small amount ofunreacted polyether, monomer and free polymer as well as the graftpolymer/polyether complex. Especially preferred are the graftpolymer/polyethers obtained from acrylonitrile and polyether triols.

The alkylene oxides employed in producing the preferred polyethersdescribed above normally have from 2 to 4 carbon atoms, inclusive whilepropylene oxide and mixtures of propylene oxide and ethylene oxide areespecially preferred.

The exact organic polyol or polyols employed as the starting materialsof this invention merely depend on the end use of the high resiliencepolyether urethane foam. For instance, the employment of polyethertriols having at least 40 mole per cent primary hydroxyl groups andmolecular weights from 2,000 to 8,000 preferably 4,000 to 7,000generally have hydroxyl numbers from 84 to 21, preferably 42 to 28 andgive primarily flexible polyether foams. The supplementary polyetherswhich may have any proportion of primary to secondary hydroxyl groupsand which may be mixed with the required polyether triols can be used tocontrol the degree of softness of the foam or vary the load bearingproperties of the foam. Such limits are not intended to be restrictive,but are merely illustrative of the large number of possible combinationsof polyether triols and other polyethers that can be employed.

The hydroxyl number is defined as the number of milligrams of potassiumhydroxide required for the complete neutralization of the hydrolysisproduct of the fully acetylated derivative prepared from 1 gram ofpolyol or mixtures of polyols with or without other crosslinkingadditives used in the invention. The hydroxyl number can also be definedby the equation: ##EQU1## wherein OH = hydroxyl number of the polyol.

A variety of organic isocyanates can be employed in the foamformulations of this invention for reaction with the organic polyolstarting materials above described to provide high resilience polyetherurethane foams. Preferred isocyanates are polyisocyanates andpolyisothiocyanates of the general formula:

    (QNCY).sub.i

wherein Y is oxygen or sulfur, i is an integer of two or more and Q isan organic radical having the valence of i. For instance, Q can be asubstituted or unsubstituted hydrocarbon radical, such as alkylene andarylene, having one or more aryl-NCY bonds and/or one or more alkyl-NCYbonds. Q can also include radicals such as --QZQ--, where Q is analkylene or arylene group and Z is a divalent moiety such as --O--,--O--Q--O--, --CO--, CO₂, --S--, --S--Q--S--, --SO₂ -- and the like.Examples of such compounds include hexamethyl diisocyanate,1,8-diisocyanateo-p-methane, xylylene diisocyanate, (OCNCH₂ CH₂ CH₂OCH₂)₂ O, 1-methyl-2, 4-diisocyanatocyclohexane, phenylenediisocyanates, tolylene diisocyanates, chlorophenylene diisocyanates,diphenylmethane-4,4'-diisocyanate, naphthalene-1,5-diisocyanate,triphenylmethane-4,4'-4"-triisocyanate, andisopropylbenzene-alpha-4-diisocyanates.

Further included among the isocyanates useful in this invention aredimers and trimers of isocyanates and diisocyanates and polymericdiisocyanates such as those having the general formula:

    (QNCY).sub.i and [Q(NCY).sub.i ].sub.j

in which i and i are integers of two or more, and/or (as additionalcomponents in the reaction mixtures) compounds of the general formula:

    L(NCO).sub.i

in which i is one or more and L is a monofunctional or polyfunctionalatom or radical. Examples of this type include ethylphosphonicdiisocyanate, C₂ H₅ P(O) (NCO)₂ ; phenylphosphonic diisocyanate, C₆ H₅P(O) (NCO)₂ ; compounds containing a =Si-NCO group, isocyanates derivedfrom sulfonamides (QSO₂ NCO), cyanic acid, thiocyanic acid, andcompounds containing a metal -NCO radical such as tributyltinisocyanate.

More specifically, the polyisocyanate component employed in thepolyurethane foams of this invention also includes the followingspecific compounds as well as mixtures of two or more of them:2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, crude tolylenediisocyanate, bis(4-isocyanatophenyl)methane, polymethylenepolyphenylisocyanates that are produced by phosgenation ofanilineformaldehyde condensation products, dianisidine diisocyanate,toluidine diisocyanate, xylylene diisocyanate,bis(2-isocyanatoethyl)-fumarate, bis(2-isocyanatoethyl) carbonate,1,6-hexamethylene-diisocyanate, 1,4-tetramethylene-diisocyanate,1,10-deca-methylene-diisocyanate, cumene-2,4-diisocyanate,4-methoxy-1,3-phenylene diisocyanate,4-chloro-1,3-phenylenediisocyanate, 4-bromo-1,3-phenylene diisocyanate,4-ethoxy-1,3-phenylene-diisocyanate, 2,4'-diisocyanato-diphenylether,5,6-dimethyl-1,3-phenylene diisocyanate,2,4-dimethyl-1,3-phenylenediisocyanate, 4,4'-diisocyanatodiphenylether,bis 5,6-(2-iso-cyanatoethyl)bicyclo [2,2,1]hept-2-ene,benzidinediisocyanate, 4,6-dimethyl-1,3-phenylenediisocyanate,9,10-anthracenediisocyanate, 4,4'-diisocyanatodibenzyl, 3,3-dimethyl-4,4'-diisocyanatodiphenylmethane, 2,6-dimethyl-4,4'-diisocyanatodiphenyl2,4-diisocyanatostilbene, 3,3'-dimethyl-4,4'-diisocyanatodiphenyl,3,3'-dimethoxy-4,4'-diisocyanatodiphenyl 1,4-anthracenediisocyanate,2,5-fluorenediisocyanate 1,8-naphthalenediisocyanate,2,6-diisocyanatobenzfuran, 2,4,6-toluenetriisocyanate, and many otherorganic polyisocyanates that are known in the art, such as those thatare disclosed in an article by Siefken, Ann., 565, 75 (1949). Ingeneral, the aromatic polyisocyanates are preferred.

Particularly useful isocyanate components of high resilience cold cureformulations within the scope of this invention are combinations ofisomeric tolylene diisocyanates and polymeric isocyanates having unitsof the formula ##SPC1##

wherein R is hydrogen and/or lower alkyl and x has a value of at least2.1. Preferably the lower alkyl radical is methyl and x has a value offrom 2.1 to about 3.0.

The amount of polyisocyanate employed will vary slightly depending onthe nature of the polyurethane being prepared. In general thepolyisocyanates are employed in the foam formulations of this inventionin amounts that provide from 80 to 150 per cent, preferably from 90 to110 per cent of the stoichiometric amount of the isocyanato groupsrequired to react with all of the hydroxyl groups of the organic polyolstarting materials and with any water present as a blowing agent. Mostpreferably, a slight amount of isocyanato groups in excess to thestoichiometric amount is employed.

The blowing agents employed in this invention include methylenechloride, water, liquefied gases which have boiling points below 80°F.and above -60°F., or by other inert gases such as nitrogen, carbondioxide, methane, helium and argon. Suitable liquefied gases includesaturated aliphatic fluorohydrocarbons which vaporize at or below thetemperature of the foaming mass. Such gases are at least partiallyfluorinated and can also be otherwise halogenated. Fluorocarbon blowingagents suitable for use in foaming the formulations of this inventioninclude trichloromonofluoromethane, dichlorodifluoromethane,dichlorofluoromethane, 1,1-chloro-1-fluoroethane, 1-chloro-1,1-difluoro,2,2-dichloroethane, and 1,1,1-trifluoro, 2-chloro-2-fluoro,3,3-difluoro-4,4,4-trifluorobutane. The amount of blowing agent usedwill vary with density desired in the foamed product. Usually from 2 to20 parts by weight of the blowing agent per 100 parts by weight of theorganic polyol starting materials are preferred.

The catalysts employed in this invention include any of the catalystused in producing conventional flexible polyurethane foam. Illustrativecatalysts are conventional amine catalysts such as N-methyl morpholine,N-ethyl morpholine, hexadecyl dimethylamine, triethylamine,N,N,N',N'-tetramethyl-1,3-butanediamine, N,N-di-methylethanol-amine,bis(2-dimethylaminoethyl)ether, N,N,N',N'-tetramethyl ethylenediamine,4,4'-methylene bis(2-chloroaniline), dimethyl benzylamine, N-cocomorpholine, triethylene diamine, [1,4-diazobicyclo (2,2,2)-octane], theformate salts or triethylene diamine, other salts or triethylene diamineand oxyalkylene adducts of primary and secondary amino groups, and thelike. If desired, conventional organo metal catalysts may be used tosupplement the amine catalysts. Illustrative of such metal catalysts arethe tin salts of various carboxylic acids e.g. stannous octoate, dibutyltin dilaurate, nickel acetylacetonates, and the like. Generally thetotal amount of catalyst employed in the mixtures will range from 0.1 to2 weight percent based on the total weight of the organic polyolstarting materials.

The relative amounts of the various components reacted in accordancewith the above described process for producing high resilience polyetherurethane foams in accordance with this invention are not narrowlycritical. The polyether and the polyisocyanate are present in the foamformulations used to produce such foams, i.e. a major amount. Therelative amounts of these two components is the amount required toproduce the urethane structure of the foam and such relative amounts arewell known in the art. The blowing agent, catalyst and siloxanes areeach present in a minor amount necessary to achieve the function of thecomponent. Thus, the blowing agent is present in a minor amountsufficient to foam the reaction mixture, the catalyst is present in acatalytic amount (i.e., an amount sufficient to catalyze the reaction toproduce the urethane at a reasonable rate) and the siloxane fluids arepresent in a foam-stabilizing amount (i.e., in an amount sufficient tostabilize the foam against voids and shrinkage). Preferred amounts ofthese various components are given hereinabove

The high resilience cold cure urethane foams produced in accordance withthis invention can be used for the same purposes as correspondingconventional hot cure polyether urethane foams, e.g. they can be usedwhere ever cushioning is desired, e.g. in furniture; in transportationsystems, automobiles, planes, etc.; in carpeting; in the packaging ofdelicate objects; and the like.

Other additional ingredients can be employed in minor amounts inproducing the high resilience polyether urethane foams in accordancewith the process of this invention, if desired, for specific purposes.Thus inhibitors (e.g. d-tartaric acid and tertiary-butyl pyrocatechol,"Ionol") can be employed to reduce any tendency of the foam tohydrolytic or oxidative instability. Flame retardants (e.g.tris(2-chloroethyl)phosphate) can be used. Dihydrocarbon silicone oils,e.g. dimethylsiloxanes, the siloxane-oxyalkylene block copolymersdescribed in U.S. application No. 84,181 filed Oct. 26, 1970, now U.S.Pat. No. 3,741,917 the aralkyl modified siloxanes described in U.S.applicaton No. 305,713 filed Nov. 13, 1972 now U.S. Pat. No. 3,839,384and the cyanealkyl modified siloxane fluids described in my copendingU.S. application Ser. No. 325,327 filed Jan. 22, 1973, now abandoned maybe mixed if desired with the siloxanes employed in this invention. Whilesuch mixtures are not required they may help expand the usefulness ofthe siloxane fluids employed herein by increasing the adaptability ofthe siloxane fluid to a variety of foam formulations. Of course anyorganic solvent for the amine catalysts, e.g. polyols such as hexyleneglycol (i.e. 2-methyl-2,4-pentanediol), dipropylene glycol, and the likecan be used which substantially do not adversely effect the operation ofthe process or reactants. Examples of other additives that can beemployed are crosslinkers such as glycerol, triethanol amine, and theiroxyalkylene adducts, and anti-yellowing agents.

An additional feature of the instant invention are the novelcompositions suitable for use in producing the high resilience polyetherurethane foam. For example it may be desirable, particularly on acommercial scale to employ the cyanoalkoxy-alkyl modified siloxane fluidin a diluted form, i.e. in the form of a siloxane fluid-solvent solutionpremix or a siloxane fluid-solvent-catalyst solution premix. Suchsolution premixtures can help serve to eliminate any mixing, metering,or settling problems. Moreover, fewer streams of ingredients may beneeded at the mixing head of the operational apparatus. Of considerableimportance is that the formulator has the latitude to select theparticular solvent which best suits the system and minimize or eliminateany loss of foam properties. Siloxane fluid-solvent-catalyst premixescan also be used since the selected solvent can be one which serves thedual role of solvent for the catalysts as well as the siloxane fluid.This option of formulating a premix simplifies the foaming operation andimproves the precision of metering ingredients. While any suitableorganic solvent such as hydrocarbon, halohydrocarbons, organic hydroxylcompounds, alkyl phthalates, and the like may be employed, preferablywhen employed the solvent selected should be one in which thecyanoalkoxy-alkyl modified siloxane fluid is substantially soluble. Forexample, it is preferred that at least five parts by weight of thecyanoalkoxy-alkyl modified siloxane oil be soluble in 95 parts by weightof solvent. More preferably the minimum percentage of cyanoalkoxy-alkylmodified siloxane fluid in the siloxane fluid-solvent or siloxanefluid-solvent-catalyst solutions should be in the range of at leastabout ten to at least about 30 weight percent. Of course it isunderstood that such solvents need not be employed and that the maximumpercentage of cyanoalkoxyalkyl modified siloxane fluid in said solventsolutions is not critical. Moreover, when employed such solventsolutions should of course be correlated to the amounts of activecyanoalkoxy-alkyl modified siloxane fluid that may be employed perhundred parts by weight of the organic polyol starting material asoutlined above. The same correlation should also be made with regard tocatalyst when a siloxane fluid-solvent-catalyst solution is employed.Preferably the solvent for the cyanoalkoxy-alkyl modified siloxane fluidis an organic hydroxyl compound such as hydroxyl terminated organicether compounds. More preferably they are polyether triols, diols, andmono-ols such as the adducts of ethylene oxide, propylene oxide,butylene oxide, with starters such as glycerol, water,trimethylolpropane, 1,2,6-hexanetriol, ethylene glycol, butanol,nonylphenol, and the like. Of course the oxyalkylene units of suchadducts may be of different types, e.g. oxypropylene and oxyethylenegroups, and may be randomly distributed or in blocks. The most preferredsolvents are the polyether triols having all or predominantlyoxypropylene units in the oxyalkylene portion and having molecularweights in the range from about 2,000 to 6,000 inasmuch as they may bethe same as, or similar to the primary triols employed as the organicpolyol starting material of the foam formulation. Moreover thisdiscovery concerning the solubility of the cyanoalkoxy-alkyl modifiedsiloxane fluids of this invention can be regulated and controlled. Forstability reasons it is preferred to use the siloxane fluids containingnon-hydrolyzable cyanoalkoxy-alkyl radicals (Si-R'OR"CN) in said solventsolutions.

In accordance with this invention, the cold cure polyether urethanefoams can be produced by any suitable technique. The preferred processis a one-step or one shot technique wherein all of the reactants arereacted simultaneously with the foaming operation. A second generalprocess is called the prepolymer process whereby a prepolymer is formedby reacting the polyether starting material with a small excess of theisocyanate and later forming the prepolymer by the reaction with wateror an inert blowing agent. Another method which can be used is thequasi-propolymer technique which involves reacting a large excess of theisocyanate with the polyether starting material and then subsequentlyfoaming this product with additional polyether in the presence of ablowing agent. Of course it is understood that the ingredients of thefoam forming formulation can be mixed in any suitable manner prior tocommencing the cure reaction. Sometimes it is preferred to employvarious premixes such as a premixture of the polyether starting materialand siloxane fluid stabilizer, a premixture of polyether startingmaterial, siloxane fluid, water and catalyst; a premixture of thepolyisocyanate and siloxane fluid, a siloxane fluid-solvent-catalystsolution as outlined above; and the like. Because of the high exothermicnature of the reaction high resilience urethane foams are rapidlyproduced without the need of any external heat by mixing the reactantsat ambient temperatures and pouring the foaming reaction mixture into asuitable mold and allowing the foam to cure itself. Of course, ifdesired the overall reaction can be even further accelerated bypreheating the mold and/or employing conventional high temperature postcuring procedures. Within a shorter period of time the cold cureprocess, with or without post cure, simultaneously achieves a greaterdegree of cure throughout the entire foam, and shorter tack free anddemolding time, then is generally achieved with conventional hot cureprocesses. For instance, cold cure foams can be removed from the moldfar sooner without substantial damage to the surface than conventionalhot cure foams. Of course, it is to be understood that the highresilience polyether urethane foams of this invention can also beprepared in slabstook form, if desired.

The following examples illustrate the present invention and are not tobe regarded as limitative. It is to be understood that the averageformulas of the siloxane fluid products are based on the mole ratios ofthe starting materials employed, "Me" represents a methyl radical,"Conc." represents concentration, "p,h.p." refers to parts ofsiloxane-solvent solution per hundred parts of organic polyol startingmaterial unless otherwise designated, "100 Index" indicates that thenumber of moles of NCO groups is equal to the total moles of hydroxylgroups in the foam formulation, "ppm" represents parts per millionparts, and that all of the parts, percentages and proportions referredto herein and in the appended claims are by weight unless otherwiseindicated.

EXAMPLE 1

Into a flask equipped with a thermometer, mechanical stirrer, condenserand nitrogen blow-by were charged about 43.8 grams of a hydrosiloxanefluid having the average formula.

    Me.sub.3 SiO(Me.sub.2 SiO).sub.15 (MeHSiO).sub.10 SiMe.sub.3

and about 31.2 grams of allyl-betacyanoethyl ether. The mixture washeated rapidly to about 85°C. with constant stirring. At thattemperature 25 ppm platinum as chloroplatinic acid was added and anexothermal reaction noted. The reaction was maintained at about 85°C. to110°C. until completion of the reaction which was signified by anegative SiH content by the fermentation tube technique involving theuse of an aqueous potassium hydroxide, ethanol solution. The reactionmixture was then cooled to about room temperature; neutralized withsodium bicarbonate and filtered. There was obtained a clear, ambercyanoalkoxy-alkyl modified siloxane fluid product having the averageformula

    Me.sub.3 SiO(Me.sub.2 SiO).sub.15 (NCC.sub.2 H.sub.4 OC.sub.3 H.sub.6 SiMeO).sub.10 SiMe.sub.3

Said siloxane fluid product had an average molecular weight of about2980 and a viscosity of about 116.6 centistokes at 25°C. and ishereinafter referred to as Siloxane A.

EXAMPLE 2

Example 1 was repeated except about 44.6 grams of a hydrosiloxane fluidhaving the average formula

    Me.sub.3 SiO(Me.sub.2 SiO).sub.3.7 (MeHSiO).sub.3.2 SiMe.sub.3

about 30.4 grams of allyl-betacyanoethyl ether, about 50 ppm platinum aschloroplatinic acid and one drop of acetic acid were used. There wasobtained a clear amber cyanoalkoxy-alkyl modified siloxane fluid producthaving the average formula

    Me.sub.3 SiO(Me.sub.2 SiO).sub.3.7 (NCC.sub.2 H.sub.4 OC.sub.3 H.sub.6 SiMeO).sub.3.2 SiMe.sub.3

Said siloxane fluid product had an average molecular weight of about 987and a viscosity of about 35.1 centistokes at 25°C. and is hereinafterreferred to as Siloxane B.

EXAMPLE 3

Example 2 was repeated except about 45.4 grams of a hydrosiloxane fluidhaving the average formula

    Me.sub.3 SiO(Me.sub.2 SiO).sub.3.8 (MeHSiO).sub.3.1 SiMe.sub.3

and about 29.6 grams of the allyl-betacyanoethyl ether were used. Therewas obtained a clear amber cyanoalkoxy-alkyl modified siloxane fluidproduct having the average formula

    Me.sub.3 SiO(Me.sub.2 SiO).sub.3.8 (NCC.sub.2 H.sub.4 OC.sub.3 H.sub.6 SiMeO).sub.3.1 SiMe.sub.3

Said siloxane fluid product had an average molecular weight of about 967and a viscosity of about 29.3 and is hereinafter referred to as SiloxaneC.

EXAMPLE 4

Example 1 was repeated except about 43.8 grams of a hydrosiloxane fluidhaving the average formula

    Me.sub.3 SiO(Me.sub.2 SiO).sub.3.6 (MeH SiO).sub.3.4 SiMe.sub.3

about 31.2 grams of the allyl-betacyanoethyl ether and 50 ppm platinumas chloroplatinic acid were used. There was obtained a clear ambercyanoalkoxy-alkyl siloxane fluid product having the average formula

    Me.sub.3 SiO(Me.sub.2 SiO).sub.3.6 (NCC.sub.2 H.sub.4 OC.sub.3 H.sub.6 SiMeO).sub.3.4 SiMe.sub.3

Said siloxane fluid product had an average molecular weight of about993, a viscosity of about 31.1 centistokes at 25°C. and is hereinafterreferred to as Siloxane D.

EXAMPLE 5

Example 2 was repeated except about 46.5 grams of a hydrosiloxane fluidhaving the average formula

    Me.sub.3 SiO(Me.sub.2 SiO).sub.3.9 (MeH SiO).sub.2.9 SiMe.sub.3

and about 28.5 grams of the allyl-betacyanoethyl ether were used. Therewas obtained a clear amber cyanoalkoxyalkyl siloxane fluid producthaving the average formula

    Me.sub.3 SiO(Me.sub.2 SiO).sub.3.9 (NCC.sub.2 H.sub.4 OC.sub.3 H.sub.6 SiMeO).sub.2.9 SiMe.sub.3

Said siloxane fluid product had an average molecular weight of about945, a viscosity of about 27.6 centistokes at 25°C. and is hereinafterreferred to as Siloxane E.

EXAMPLE 6

Example 2 was repeated except about 45.7 grams of a hydrosiloxane fluidhaving the average formula

    Me.sub.3 SiO(Me.sub.2 SiO).sub.3.8 (MeHSiO).sub.3.0 SiMe.sub.3

about 29.3 grams of the allyl-betacyanoethyl ether and 25 ppm platinumas chloroplatinic acid were used. There was obtained a clear ambercyanoalkoxy-alkyl siloxane fluid product having the average formula

    Me.sub.3 SiO(Me.sub.2 SiO).sub.3.8 (NCC.sub.2 H.sub.4 OC.sub.3 H.sub.6 SiMeO).sub.3.0 SiMe.sub.3

Said siloxane fluid product had an average molecular weight of about960, a viscosity of about 29.3 centistokes at 25°C. and is hereinafterreferred to as Siloxane F.

EXAMPLE 7

Example 1 was repeated except about 31.3 grams of a hydrosiloxane fluidhaving the average formula

    Me.sub.3 SiO(Me.sub.2 SiO).sub.4.0 (MeHSiO).sub.2.8 SiMe.sub.3

about 15.37 grams of the allyl-betacyanoethyl ether and 10 ppm platinumas chloroplatinic acid were used. There was obtained a clear ambercyanoalkoxy-alkyl modified siloxane fluid product having the averageformula

    Me.sub.3 SiO(Me.sub.2 SiO).sub.4.0 (NC C.sub.2 H.sub.4 OC.sub.3 H.sub.6 OSiMeO).sub.2.8 SiMe.sub.3

Said siloxane fluid product had an average molecular weight of about 935and is hereinafter referred to as Siloxane G.

EXAMPLE 8

Example 1 was repeated except about 47.2 grams of a hydrosiloxane fluidhaving the average formula

    Me.sub.3 SiO(Me.sub.2 SiO).sub.3.2 (MeHSiO).sub.2.3 SiMe.sub.3

about 27.8 grams of the allyl-bectacyanoethyl ether and about 30 cc's.of xylene as a solvent were used. There was obtained a clear ambercyanoalkoxy-alkyl modified siloxane fluid product having the averageformula

    Me.sub.3 SiO(Me.sub.2 SiO).sub.3.2 (NC C.sub.2 H.sub.4 OC.sub.3 H.sub.6 SiMeO).sub.2.3 SiMe.sub.3

Said siloxane fluid product had an average molecular weight of about781, a viscosity of about 19.1 centistokes at 25°C. and is hereinafterreferred to as Siloxane H.

EXAMPLE 9

Example 6 was repeated except about 49 grams of a hydrosiloxane fluidhaving the average formula

    Me.sub.3 SiO(Me.sub.2 SiO).sub.2.3 (MeH SiO).sub.1.8 SiMe.sub.3

and about 26 grams of the allyl-betacyanoethyl ether were used. Therewas obtained a clear amber cyanoalkoxy-alkyl modified siloxane fluidproduct having the average formula

    Me.sub.3 SiO(Me.sub.2 SiO).sub.2.3(NC C.sub.2 H.sub.4 OC.sub.3 H.sub.6 SiMeO).sub.1.8 SiMe.sub.3

Said siloxane fluid product had an average molecular weight of about631, a viscosity of about 13.4 centistokes at 25°C. and is hereinafterreferred to as Siloxane I.

EXAMPLE 10

Example 6 was repeated except about 61.4 grams of a hydrosiloxane fluidhaving the average formula

    Me.sub.3 SiO(Me.sub.2 SiO).sub.2.5 (MeH SiO).sub.1.5 SiMe.sub.3

and about 28.6 grams of the allyl-betacyanoethyl ether were used. Therewas obtained a clear amber cyanoalkoxyalkyl modified siloxane fluidproduct having the average formula

    Me.sub.3 SiO(Me.sub.2 SiO).sub.2.5 (NC C.sub.2 H.sub.4 OC.sub.3 H.sub.6 SiMeO).sub.1.5 SiMe.sub.3

Said siloxane fluid product had an average molecular weight of about604, a viscosity of about 11.6 centistokes at 25°C. and is hereinafterreferred to as Siloxane J.

EXAMPLE 11

Example 2, was repeated except about 54.5 grams of a hydrosiloxane fluidhaving the average formula

    Me.sub.3 SiO(Me.sub.2 SiO).sub.2.1 (MeH SiO) SiMe.sub.3

about 20.5 grams of the allyl-betacyanoethyl ether and about 30 ppmplatinum as chloroplatinic acid were used. There was obtained acyanoalkoxy-alkyl modified siloxane fluid product having the averageformula

    Me.sub.3 SiO(Me.sub.2 SiO).sub.2.1 (NCC.sub.2 H.sub.4 OC.sub.3 H.sub.6 SiO) SiMe.sub.3

Said siloxane fluid product had an average molecular weight of about488, a viscosity of about 7.1 centistokes at 25°C. and is hereinafterreferred to as Siloxane K.

EXAMPLE 12

Example 2 was repeated except about 45.4 grams of a hydrosiloxane fluidhaving the average formula

    Me.sub.3 SiO(Me.sub.2 SiO).sub.4.9 (MeHSiO).sub.4.1 SiMe.sub.3

about 29.6 grams of the allyl-betacyanoethyl ether, about 75 grams oftoluene as solvent and about 20 ppm platinum as chloroplatinic acid wereused. There was obtained a clear amber cyanoalkoxy-alkyl siloxane fluidproduct having the average formula

    Me.sub.3 SiO(Me.sub.2 SiO).sub.4.9 NCC.sub.2 H.sub.4 OC.sub.3 H.sub.6 SiMeO).sub.4.1 SiMe.sub.3

Said siloxane fluid product had an average molecular weight of about1235, and is hereinafter referred to as Siloxane L.

EXAMPLE 13

Example 12 was repeated except about 45.9 grams of a hydrosiloxane fluidhaving the average formula

    Me.sub.3 SiO(Me.sub.2 SiO).sub.4.2 (MeHSiO).sub.3.7 SiMe.sub.3

and about 29.6 grams of the allyl-betacyanoethyl ether were used. Therewas obtained a clear amber cyanoalkoxy-alkyl modified siloxane fluidproduct having the average formula

    Me.sub.3 SiO(Me.sub.2 SiO).sub.4.2 (NC C.sub.2 H.sub.4 OC.sub.3 H.sub.6 SiMeO)SiMe.sub.3

Said siloxane fluid product had an average molecular weight of about1115 and is hereinafter referred to as Siloxane M.

EXAMPLE 14

Example 1 was repeated except about 49.8 grams of a hydrosiloxane fluidhaving the average formula

    Me.sub.3 SiO(Me.sub.2 SiO).sub.3.3 (MeHSiO).sub.2.0 SiMe.sub.3

about 25.2 grams of the allyl-betacyanoethyl ether and about 75 grams oftoluene as solvent were used. There was obtained a clear ambercyanoalkoxy-alkyl modified siloxane product having the average formula

    Me.sub.3 SiO(Me.sub.2 SiO).sub.3.3 NCC.sub.2 H.sub.4 OC.sub.3 H.sub.6 SiMeO).sub.2.0 SiMe.sub.3

Said siloxane fluid product had an average molecular weight of about 748and is hereinafter referred to as Siloxane N.

EXAMPLE 15

Example 14 was repeated except about 47 grams of a hydrosiloxane fluidhaving the average formula

    Me.sub.3 SiO(Me.sub.2 SiO).sub.3.0 (MeH SiO).sub.2.4 SiMe.sub.3

and about 28 grams of the allyl-betacyanoethyl ether were used. Therewas obtained a clear amber cyanoalkoxy-alkyl modified siloxane fluidproduct having the average formula

    Me.sub.3 SiO(Me.sub.2 SiO).sub.3.0 NCC.sub.2 H.sub.4 OC.sub.3 H.sub.6 SiMeO).sub.2.4 SiMe.sub.3

Said siloxane fluid product had an average molecular weight of about 786and is hereinafter referred to as Siloxane O.

For the sake of brevity the above designations given for the siloxanefluids along with the following designations are used to denote thevarious ingredients employed in the following examples.

                  TABLE 1                                                         ______________________________________                                        Designation                                                                   Organic Polyols                                                                               Composition                                                   ______________________________________                                        E1            This is a Polyether triol, mol.                                               wt. about 6,000; hydroxyl No.                                                 about 27; containing about 85                                                 mole% primary hydroxyl groups                                                 produced by reacting about 89%                                                propylene oxide and about 11%                                                 ethylene oxide with glycerol.                                   E2            This is a polyether triol, mol.                                               wt. about 5,000; hydroxyl No.                                                 about 34; containing about 75                                                 mole% primary hydroxyl groups                                                 produced by reacting about 84%                                                propylene oxide and about 16%                                                 ethylene oxide with glycerol.                                   E3            This is a graft polymer/polyol;                                               about 80 wt.% polyol, 10 wt.%                                                 styrene and 10 wt.% acryloni-                                                 trile; having a hydroxyl No.                                                  of about 28, produced by poly-                                                merizing styrene and acryloni-                                                trile in E2.                                                    Polyisocyanates                                                                               Composition                                                   ______________________________________                                        C1            This is a mixture of about 80                                                 wt.% 2,4-tolylene diisocyanate                                                and about 20 wt.% 2.6-toluene                                                 diisocyanate.                                                   C2            This is a polymethylene poly-                                                 phenyl isocyanate polymer                                                     containing about 2.6-2.9 moles                                                of NCO per mole of polymer and                                                having an isocyanate content                                                  of about 31.4 percent.                                          C3            This is a composition of about                                                80 wt.% C1 and about 20 wt.%                                                  C2.                                                             Catalyst        Composition                                                   A1            This is a composition consist-                                                ing of about 70 wt.% bis                                                      (N,N-dimethylaminoethyl) ether                                                and about 30 wt.% dipropylene                                                 glycol solvent.                                                 Siloxane Solvents                                                                             Composition                                                   S1            This is a polyether triol, mol.                                               wt. about 3000 produced by re-                                                acting propylene oxide with                                                   glycerol, and a hydroxyl number                                               of about 56.                                                    ______________________________________                                    

EXAMPLE 16

The foam formulations employed in producing the foams in this examplewere identical save for variations in the amount of cyanoalkoxy-alkylmodified siloxane fluid employed. The high resilience polyether urethanefoams were all prepared and evaluated in the following manner.

A blend of polyether triols E2 and E3 was dispersed into a paper cup atabout 20° to 30°C. Then the siloxane fluid and dibutyltin-dilauratecatalyst were added via a 5 cc syringe and dispersed with a spatulafollowed by a premix of water, A1 catalyst, solid triethylenediamine andN-ethylmorpholine catalyst which was also dispersed in the mixturewithout using a baffle. The mixture was then placed under a drill pressmixer and agitated for about 10 seconds at 2150 rpm, while the cup wasturned around to insure proper mixing. Without stopping the drill presspolyisocyanate C3 was rapidly added and mixed for about seven seconds.The foam forming mixture was then rapidly poured into an 8 inch × 8 inch× 6 inch parchment lined cake box which was supported by a wooden moldand allowed to cure. The high resilience polyether urethane foam productwas allowed to rest for at least two minutes after completion of thefoam rise to avoid densification at the bottom of the foam bun.Thereafter the foam while still in the cake box was placed in an oven at125°C. for about ten minutes to reduce tackiness and facilitateseparation of the paper liner from the mold and cutting of the foamsamples. The foam was allowed to stand for about one hour before cuttingwhen it was then sliced one and one-half inches from the bottom with aband saw.

Said foam formulations all contained 100 parts by weight of thepolyether blend on the order of about 60 parts (150 grams) of polyethertriol E2 and 40 parts (100 grams) of polyether triol E3; about 2.6 partsby weight (6.5 grams) of water; about 0.1 parts by weight (0.25 grams)of amine catalyst A1; about 1.2 parts by weight (3.0 grams) ofN-ethylmorpholine catalyst; about 0.12 parts by weight (0.3 grams) ofsolid triethylene diamine catalyst; about 0.015 parts by weight (0.038grams) of dibutyltindilaurate catalyst and about 33.9 parts by weight(84.8 grams) of polyisocyanate C3 (100 Index). The cyanoalkoxy-alkylmodified siloxane fluid was used in the form of a siloxane fluid-solventsolution composed of about 22 parts by weight of siloxane fluid and 78parts by weight of solvent S1. The amount and particular siloxane fluidemployed was varied and the recorded properties of the various foamsamples are given in TABLE 2 below.

The breathability measurements were all recorded by a Gurley Densometerwhich measures the porosity or air resistance of the foam as shown bythe time in seconds for a given volume of air (300 cc's of air) to passinto a standard area of foam. The value recorded is the average value offive such measurements given in seconds per 300 cc's of displaced air.

                                      TABLE 2                                     __________________________________________________________________________    Foam                                                                              Siloxane                                                                             Siloxane   Foam    Cells/                                          No. Fluid No.                                                                            Conc. (php)                                                                              Breathability                                                                         Inch                                                                              Shrinkage                                                                           Cell Uniformity                       __________________________________________________________________________     A  Control                                                                              None       4.7     16  None  Severe Voids - Irregular               1  A      0.2        9.0     30  None  Slight Voids - Irregular               2  A      0.3        8.4     29  None  Very Slight Voids - Irregular          3  A      0.35       --      --  Slight                                                                              No Voids - Uniform                     4  A      0.75       37.6    34  Moderate                                                                            No Voids - Uniform                     5  B      0.3        6.4     25  None  Moderate Voids - Irregular             6  B      0.75       6.5     26  None  Slight Voids - Irregular               7  B      1.12       8.3     28  None  No Voids - Uniform                     8  C      0.3        4.6     26  None  Moderate Voids - Irregular             9  C      0.75       5.7     26  None  Moderate Voids - Irregular            10  C      1.12       10      28  None  Moderate Voids - Irregular            11  D      0.3        5.5     22  None  Severe Voids - Irregular              12  D      0.75       5.8     24  None  Moderate Voids - Irregular            13  D      1.12       8.3     26  None  Very Slight Voids - Irregular         14  E      0.3        4.6     24  None  Slight Voids - Irregular              15  E      0.75       8.1     26  None  No Voids - Uniform                    16  E      1.12       12.5    30  None  No Voids - Uniform                    17  F      0.3        4.5     24  None  Moderate Voids - Irregular            18  F      0.75       7.3     26  None  No Voids - Uniform                    19  F      1.12       11.7    30  None  No Voids - Uniform                    20  H      0.3        6.3     24  None  Moderate Voids - Irregular            21  H      0.75       8.2     28  None  Very Slight Voids - Irregular         22  H      1.12       10.2    30  None  No Voids - Uniform                    23  I      0.3        6.3     22  None  Moderate Voids - Irregular            24  I      0.75       7.3     25  None  Slight Voids - Irregular              25  I      1.12       9.1     24  None  Very Slight Voids - Irregular         26  J      0.3        6.1     24  None  Moderate Voids - Irregular            27  J      0.75       7.7     26  None  Slight Voids - Irregular              28  J      1.12       11.0    28  None  No Voids - Uniform                    29  K      0.75       7.0     26  None  Severe Voids - Irregular              30  K      1.12       7.5     24  None  Moderate Voids - Irregular            31  K      2.50       10.7    30  None  No Voids - Uniform                    __________________________________________________________________________

EXAMPLE 17

Another series of high resilience polyether urethane foam was producedin the same manner as Example 16 except that the foam formulations allcontained 100 parts by weight of the polyether blend on the order ofabout 50 parts (100 grams) of polyether triol E1 and about 50 parts (100grams) of polyether triol E3; about 2.7 parts (5.4 grams) of water;about 0.08 parts (0.16 grams) of amine catalyst A1; about 0.8 parts ofN-ethyl-morpholine catalyst; about 0.15 parts (0.30 grams) of solidtriethylenediamine catalyst; about 0.033 parts (0.066 grams) ofdibutyltindilaurate catalyst, about 5.7 parts (11.4 grams) oftrichlorofluoromethane blowing agent; and about 34.1 parts (58.2 grams)of polyisocyanate C3 (100 Index). The cyanoalkoxy-alkyl modifiedsiloxane fluid was used in the form of a siloxane fluidsolvent solutioncomposed of about 10 parts by weight of siloxane fluid and 90 parts byweight of solvent S 1. The amount and particular siloxane employed wasvaried and the recorded properties of the various foam samples are givenin TABLE 3 below.

                                      TABLE 3                                     __________________________________________________________________________    Foam                                                                              Siloxane                                                                             Siloxane Soluton                                                                         Gurley Foam                                                                           Cells/                                          No. Fluid No.                                                                            Conc. (php.)                                                                             Breathability                                                                         Inch                                                                              Shrinkage                                                                           Cell Uniformity                       __________________________________________________________________________    A   Control                                                                              None       1.9     12  None  Severe Voids - Irregular              1   G      0.8        3.9     18  None  Moderate Voids - Irregular            2   G      2.0        5.1     24  None  Slight Voids - Irregular              3   G      3.0        5.2     24  None  Moderate Voids - Irregular            4   J      0.8        3.9     18  None  Moderate Voids - Irregular            5   J      2.0        5.1     24  None  Slight Voids - Irregular              6   J      3.0        5.2     24  None  Slight Voids - Irregular              7   L      0.8        3.7     20  None  Moderate Voids - Irregular            8   L      2.0        4.6     24  None  Very Slight Voids - Irregular         9   L      3.0        7.7     28  None  No Voids - Uniform                    10  M      2.0        5.6     24  None  Slight Voids - Irregular              11  N      0.8        4.3     20  None  Slight Voids - Irregular              12  N      2.0        6.4     24  None  No Voids - Uniform                    13  N      3.0        9.0     26  None  No Voids - Uniform                    14  O      0.8        4.7     18  None  Slight Voids - Irregular              15  O      2.0        4.8     22  None  No Voids - Uniform                    16  O      3.0        6.2     26  None  No Voids - Uniform                    __________________________________________________________________________

EXAMPLE 18

Example 1 was repeated except about 435 grams of a hydrosiloxane fluidhaving the average formula

    Me.sub.3 SiO(Me.sub.2 SiO).sub.3.0 (MeHSiO).sub.0.85 SiMe.sub.3

and about 97 grams of allyl-betacyanoethyl ether were used. There wasobtained a clear amber cyanoalkoxy-alkyl modified siloxane fluid producthaving the average formula

    Me.sub.3 SiO(Me.sub.2 SiO).sub.3.0 NCC.sub.2 H.sub.4 OC.sub.3 H.sub.6 SiMeO).sub.0.85 SiMe.sub.3

Said siloxane fluid product had an average molecular weight of about 530and a viscosity of about 6.39 centistokes at 25°C. and is hereinafterreferred to as Siloxane P.

EXAMPLE 19

Example 1 was repeated except about 408 grams of a hydrosiloxane fluidhaving the average formula

    Me.sub.3 SiO(Me.sub.2 SiO).sub.2.43 (MeHSiO).sub.1.1 SiMe.sub.3

and about 128 grams of allyl-betacyanoethyl ether were used. There wasobtained a clear amber cyanoalkoxy-alkyl modified siloxane fluid producthaving the average formula

    Me.sub.3 SiO(Me.sub.2 SiO).sub.2.43 NCC.sub.2 H.sub.4 OC.sub.3 H.sub.6 SiMeO).sub.1.1 SiMe.sub.3

Said siloxane fluid product had an average molecular weight of about 540and a viscosity of about 6.8 centistokes at 25°C. and is hereinafterreferred to as Siloxane Q.

EXAMPLE 20

Another series of high resilence polyether urethane foam was produced ina similar manner as described in Example 16. The foam formulations allcontained 100 parts by weight of the polyether blend on the order ofabout 60 parts of polyether triol E2 and 40 parts of polyether triol E3;about 2.6 parts by weight of water; about 0.1 parts by weight of aminecatalyst A1; about 1.2 parts by weight of a catalyst compositionconsisting of about 33 wt. percent3-dimethylamino-N,N-dimethyl-propionamide and about 67 wt. percentTergitol TP-9 (nonylphenol ± 9 moles of ethylene oxide); about 0.015parts by weight of dibutytindilaurate catalyst and about 34.03 parts byweight of polyisocyanate C3(100 Index). The cyanoalkoxy-alkyl modifiedsiloxane fluid was used in the form of a siloxane fluid-solvent solutioncomposed of about 22 parts by weight of siloxane fluid and 78 parts byweight of solvent S1. The amount and particular siloxane fluid employedwas varied and the recorded properties of the various foam samples aregiven in Table 4 below.

                                      TABLE 4                                     __________________________________________________________________________    Foam                                                                              Siloxane                                                                             Siloxane Solution                                                                        Foam                                                    No. Fluid No.                                                                            Conc. (php)                                                                              Breathability                                                                         Shrinkage                                                                           Cell Uniformity                           __________________________________________________________________________    A   Control                                                                              None       4.7     None  Severe voids - irregular                  1   P      0.2        9.2     None  No Voids - slightly coarse                2   P      0.3        9.5     None  No voids - uniform                        3   P      0.5        15.7    None  No voids - uniform                        4   P       0.75      22      None  No voids - uniform                        5   Q      0.2        6.2     None  No voids - Slightly coarse                6   Q      0.3        8.1     None  No voids - uniform                        7   Q      0.5        11.2    None  No voids - uniform                        8   Q       0.75      13.7    None  No voids - uniform                        __________________________________________________________________________

The above data in Examples 16, 17 and 20 demonstrates that the irregularcell structure and voids of the control foams can be eliminated or atleast greatly reduced by employing the siloxane fluid stabilizers ofthis invention without causing any foam shrinkage. Note that Siloxanefluid A, not of this invention, improved the cell structure byeliminating voids but also introduced the new disadvantage of foamshrinkage and is therefore unsatisfactory. The data for Siloxane fluidsD, g, I and J indicate that the voids will be eliminated withoutintroducing foam shrinkage when the proper amount of siloxane fluid isemployed. The data for Siloxane fluid C is considered to be the resultof experimental error in view of the successful results of essentiallythe same Siloxane fluids E and F.

In cases of slight foam shrinkage the normally smooth regular crown isslightly puckered and wrinkled while in cases of moderate foam shrinkageit is substantially puckered and wrinkled. This surface shrinkage isrelated to an abnormal quantity of closed cells and tight foam which inturn adversely effects the foams properties such as its resiliency,compression set and load bearing. In cases of severe shrinkage the abovedefects and disadvantages are even more aggravated and pronounced. Inaddition severe shrinkage is further evidenced by a pulling away of thefoam from the sides and/or bottom of the mold. Thus it is obvious thatreasonable amounts of the siloxane fluids of this invention can beemployed in the production of high resilience polyether urethane foamwhereas such is not the case with the siloxane fluids not of thisinvention.

Various modifications and variations of this invention will be obviousto a worker skilled in the art and it is to be understood that suchmodifications and variations are to be included within the purview ofthis application and the spirit and scope of the appended claims.

What is claimed is:
 1. A process for producing high resilience polyether urethane foam, said process comprising foaming and reacting a mixture comprising:I. organic polyol selected from the group consisting of (A) a polyether triol containing at least 40 mole per cent primary hydroxyl groups and having a molecular weight from about 2,000 to about 8,000 and (B) a mixture of said polyether triol and another polyether having an average of at least two hydroxyl groups, said polyether triol of said mixture amounting to at least 40 weight per cent of the total polyol content; Ii. organic polyisocyanate, said organic polyol and said polyisocyanate being present in the mixture in a major amount and in the relative amount required to produce the urethane; Iii. blowing agent in a minor amount sufficient to foam the reaction mixture; Iv. a catalytic amount of catalyst for the production of the urethane; and V. a cyanoalkoxy-alkyl modified siloxane fluid having the average formula

    (X).sub.z R.sub.3-z SiO(R.sub.2 SiO).sub.x [(X) (R)SiO].sub.y SiR.sub.3-z X.sub.z

wherein x has a value of 2 to 6 inclusive; y has a value of 0 to 6 inclusive; z has a value of 0 to 1 inclusive; R is a lower alkyl or phenyl radical; and X is a cyanoalkoxy-alkyl radical having the formula --(O)_(n) R'OR"CN where n has a value of 0 or 1, R' is an alkylene radical having from 3 to 8 carbon atoms and R" is an alkylene radical having from 2 to 4 carbon atoms said siloxane containing at least one of said cyanoalkoxy-alkyl radicals and having an average molecular weight in the range of about 400 to about 2000, in an amount sufficient to stabilize the foam against voids and shrinkage.
 2. A process as defined in claim 1 wherein the catalyst is an amine catalyst, or a mixture of an organic metal catalyst and an amine catalyst.
 3. A process as defined in claim 1 wherein the blowing agent is selected from the group consisting of water, a fluorocarbon compound, and mixtures thereof.
 4. A process as defined in claim 1 wherein the polyisocyanate is selected from the group consisting of tolylene diisocyanate, polymethylene polyphenyl polymeric isocyanate, and mixtures thereof.
 5. A process as defined in claim 1 wherein a minor amount of an additional ingredient selected from the group consisting of a flame retardant agent, an organic solvent for the amine catalyst, an organic solvent for the cyanoalkoxy-alkyl modified siloxane fluid, and mixtures thereof are also present in the reaction mixture.
 6. A process as defined in claim 1 wherein the cyanoalkoxy-alkyl modified siloxane fluid is employed in the form of a siloxane fluid-organic solvent solution.
 7. A process as defined in claim 6 wherein the organic solvent for the siloxane fluid is an organic polyether selected from the group consisting of monool, diol and triol hydroxy compounds, and mixtures thereof.
 8. A process as defined in claim 7 wherein the organic solvent is polyether triol.
 9. A process as defined in claim 6 wherein a catalyst is present as an additional ingredient in the siloxane fluid-organic solvent solution.
 10. A process as defined in claim 1 wherein the organic polyol polyether triol contains from about 60 to 90 mole per cent primary hydroxyl groups and has a molecular weight from about 4,000 to 7,000.
 11. A process as defined in claim 10 wherein the organic polyol is a mixture of said polyether triol and another polyether having an average of at least two hydroxyl groups said polyether triol of said mixture amounting to at least 40 weight per cent of the total polyol content.
 12. A process as defined in claim 10 wherein the other polyether is a graft acrylonitrile/polyether triol.
 13. A process as defined in claim 10 wherein the cyanoalkoxy-alkyl modified siloxane fluid has an average molecular weight of about 500 to 1000; wherein R is a lower alkyl radical, X has a value of 2 to 4 inclusive, y has a value of 1 to 4 inclusive, is n is 0 and z is
 0. 14. A process as defined in claim 13 wherein R is methyl.
 15. A process as defined in claim 14 wherein X is a 3-(2-cyanoethoxy)propyl radical.
 16. A process as defined in claim 10 wherein the cyanoalkoxy-alkyl modified siloxane fluid has an average molecular weight of about 500 to 1000; wherein R is a lower alkyl radical, x has a value of 2 to 4 inclusive, n is 0 and z is
 1. 17. A process as defined in claim 16 wherein R is a methyl radical.
 18. A process for producing high resilience polyether urethane foam, said process comprising foaming and reacting a mixture comprising:I. an organic polyol mixture of a polyether triol, said triol containing 60 to 90 mole per cent primary hydroxyl groups and having a molecular weight from about 4,000 to 7,000 and another polyether having an average of at least two hydroxyl groups, and polyether triol of said mixture amounting to at least 40 weight per cent of the total polyol content; Ii. a polyisocyanate selected from the group consisting of tolylene diisocyanate, polymethylene polyphenyl polymeric isocyanate, and mixtures thereof, said isocyanate being present in an amount from 90 to 105 percent of the amount required to provide the stoichiometric amount of isocyanate groups required to react with the hydroxyl groups of the organic polyol mixture and any water present as a blowing agent; Iii. from 2 to 20 parts by weight per 100 parts by weight of the organic polyol mixture starting material of at least one blowing agent selected from the group consisting of water and fluorocarbon blowing agents; Iv. a catalytic amount of an amine catalyst or a mixture of an organic metal catalyst and an amine catalyst; and V. about 0.08 to about 0.6 parts by weight per 100 parts by weight of the organic polyol mixture starting material of a cyanoalkoxy-alkyl modified siloxane fluid as defined in claim
 13. 19. A process as defined in claim 18 wherein R is a methyl radical.
 20. A process as defined in claim 19 wherein X is a 3-(2-cyanoethoxy)propyl radical.
 21. A process as defined in claim 18 wherein the cyanoalkoxy-alkyl modified siloxane fluid has the average formula ##EQU2## wherein Me is a methyl radical.
 22. A process as defined in claim 18 wherein the cyanoalkoxy-alkyl modified siloxane fluid has the average formula ##EQU3## wherein Me is a methyl radical.
 23. A process as defined in claim 18 wherein the cyanoalkoxy-alkyl modified siloxane fluid has the average formula ##EQU4## wherein Me is a methyl radical.
 24. A process as defined in claim 18 wherein the cyanoalkoxy-alkyl modified siloxane fluid is used in the form of a siloxane fluid-organic solvent solution.
 25. A process as defined in claim 24 wherein the organic solvent for the siloxane fluid is an organic polyether selected from the group consisting of mono-ol, diol and triol hydroxy compounds, and mixtures thereof.
 26. A process as defined in claim 25 wherein the organic solvent is polyether triol.
 27. A process as defined in claim 24 wherein a catalyst is present as an additional ingredient in the siloxane fluid-organic solvent solution. 